CN1538941A - Method for inhibiting calcium salt scale - Google Patents

Method for inhibiting calcium salt scale Download PDF

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Publication number
CN1538941A
CN1538941A CNA028155025A CN02815502A CN1538941A CN 1538941 A CN1538941 A CN 1538941A CN A028155025 A CNA028155025 A CN A028155025A CN 02815502 A CN02815502 A CN 02815502A CN 1538941 A CN1538941 A CN 1538941A
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phosphonic acid
acid ester
general formula
composition
black liquor
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CN1250463C (en
Inventor
J��O������ɭ
J·O·汤普森
S·P·弗雷特
�������ɭ
S·J·西弗森
J·E·洛伊
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Sam Fuchs trade limited liability company
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Solutia Inc
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/226—Use of compounds avoiding scale formation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
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Abstract

Compositions and method of improving inhibition of calcium salt scale formation under the conditions found in chemical pulp processes in which an effective amount of selected phosphonates or phosphonate blends is admixed with the black liquor composition recovered from the digester in a chemical pulping process. The compositions and method are especially well suited for use in the Kraft pulping process.

Description

The method that suppresses the calcium salt dirt
Technical field
The present invention relates to be used for suppress the composition and the method for the aqueous alkaline system fouling of chemical pulping process.The invention still further relates to the formation, deposition and adherent composition and the method that are used for suppressing chemical pulping process equipment calcium salt scale deposit.More particularly, the present invention relates to suppress formation, deposition and the adherent composition and the method for calcium salt scale deposit in the chemical pulping process black liquor recovery operation.
Background technology
Paper is widely used in commerce and family in the world, has various purposes.Thereby slurrying is implemented with big technical scale in the whole world, is producing the paper of enough consumptions.So this kind slurrying operation is if can implement in cost-effective efficient operation mode, its producing apparatus time compole extremely short, pulping process equipment inefficient operation stoppage time is short, and that will be desired.
The basic step of industry slurrying is that vegetable fibre is converted into wood chip, changes wood chip into slurry and moors, and (randomly) bleached pulp pool, the detergent milk pool also will be starched the paper that pool is converted into the paper product form that is fit to use, for example, writing paper, newsprinting paper and document paper.
With regard to the typical case, there are several chemical pulping methods to can be used for industrial slurrying operation.Famous industrial alkaline chemical pulping method comprises sulphate process, soda and alkali sulfite process.The highest slurry of fibre strength was moored in the middle of sulphate process produced ownership system paste-making method, and why it is to use the widest pulping process partly because it can reclaim the boiling chemical efficiently.Though the present invention is applicable to any above-mentioned alkali electroless pulping method, it is particularly useful for sulphate process also, therefore, describes sulphate process below in greater detail.
At first, gather in the crops suitable trees, suitable thin slice of size or wood chip are chipped in peeling subsequently.These wood chips are through selecting materials, and remove little and big wood chip.The suitable wood chip that stays put into subsequently pulp digester (it be a kind of container that wood chip and moisture boiling composition be housed or jar, this kind jar can be designed to intermittently or the operate continuously mode).
For example, in the batch-type pulp digester, wood chip and " rare black liquor ", that is, from the waste liquid of former pulp digester boiling, and " white liquid ", be a kind of sodium hydroxide and sodium sulfide solution, can be new preparation or from the mixture of chemical recovery device, with being pumped in the pulp digester.In digesting technoloy, the lignin that xylon is combined is dissolved in the white liquid, thereby forms slurry pool and black liquor.
With the pulp digester sealing, the pulp digester composition under high pressure is heated to suitable boiling temperature.Specified temp and pressure in pulp digester (H-coefficient) are down through after the specified time, and pulp digester material (slurry pool and black liquor) is transferred in the remaining tank.Slurry pool in remaining tank is transferred in the brown stock washers, and liquid (black liquor that forms in pulp digester) then is sent to black liquor recovery operation, i.e. Black Liquid Evaporator.Black liquor adopts, multiple-effect evaporator for example, be evaporated to highly filled, usually between 60～80% solids.Solids content is high more, and pump suction black liquor is difficult more, and the fouling problem that the pulp mill runs into is just many more.One of problem that bothers most is each operation in the pulp mill, comprises pulp digester, black liquor vaporizing operation and floats the lime carbonate dirt that forms in the preceding pulp washing operation.
Most of industrial paper mills adopt multiple-effect evaporator (MEE) as Black Liquid Evaporator.These vaporizers generally from 4 to 8 are imitated length.Generally speaking, Tao Yan calcium carbonate scaling only appears in one or two effects.At present, most factories do not use any fouling inhibitor, but by stopping Black Liquid Evaporator workshop section and rinse out the lime carbonate dirt with hot acid, i.e. pickling tackles fouling problem.This kind hot acid boils paper plant is had a negative impact, and because the acid of using has corrosion to factory's pipeline and equipment, so be a hidden danger.
Kraft cooking is a high alkalinity, generally has 10～14, particularly 12～14 pH value.The pulp digester composition contains a large amount of sodium sulphite, is used as the accelerator that increases the delignification of boiling speed.Thereby the result of its effect is the lignin that discharges in the wood chip makes Mierocrystalline cellulose be become the slurry pool.
All set of operating conditions help the formation of dirt and deposition and aggravation lime carbonate dirt and form, deposit and adhere to metal and other lip-deep tendency that it touched in the sulphate process.Under this kind processing condition, exist in the water and the calcium that sweetens off from the timber of sulphate process can react with carbonate and fouling at a good pace, produce the lime carbonate dirt deposition.This kind dirt often be deposited on Black Liquid Evaporator, pulp digester and associated conduit, heat exchanger etc. every have that lime carbonate can deposit and the equipment on adherent surface in.This kind deposition is passed in time and is accumulated, and can cause the pulping production line downstream to stop too early, in order that fall dirt deposition with the hot acid eccysis.
Some patents and technical article once disclosed scale problems.In " a kind of highly effective chelating agent is in the application aspect the fouling of control pulp digester ", R.H.Windhager, " paper-making industry magazine " pp.42～44, in 1973-11-05 one literary composition, a small amount of mono amino methylene phosphonic acid (ATMP) is disclosed as the application of the inhibition of the lime carbonate fouling inhibitor in the pulp digester from the fouling of pulp digester cooking liquor.
United States Patent (USP) 4,799,995 (authorize people such as Druce K.Crump, 1989-01-24) open, starch the inhibition of mooring calcium dirt under the pulp digester interior condition and realize by in slurrying liquid, adding the sour mixture of poly-amino (polyalkylene phosphine) with nonionogenic tenside.This United States Patent (USP) is also open, phosphonic acid ester such as nitrilo three (methylene phosphonic acid) (" NTMP " or " ATMP "), 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid (" HEDP ") and 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid sodium (" NaHEDP ") allegedly jointly are used to control dirt.Yet, ' 995 patent is open, in fact the use of HEDP in black liquor promoted fouling, and diethylenetriamine five (methylene phosphonic acid) (" DTPMP ") uses in black liquor, only produces limited dirt and reduce effect when not having nonionogenic tenside.Though ' 995 patent disclosure the application of nonionogenic tenside can improve the effect that reduces dirt, preferably avoid in the chemical pulping method, using tensio-active agent, particularly in pulp digester.Composition of the present invention in the time of in joining alkali electroless pulping process pulp digester, can suppress the fouling of calcium salt in chemical pulping is produced effectively, and not need nonionogenic tenside.
Canadian Patent 1,069,800 (people such as Philip S.Davis, 1980-01-15) be disclosed in and add Organophosphonate in the black liquor, for example, 1-hydroxy ethylidene-1,1-di 2 ethylhexyl phosphonic acid (HEDP) and amino-Organophosphonate, for example, amino three (methylene phosphonic acids) (AMP), ethylene diamine four (methylene phosphonic acid) (EDTPA) and hexamethylene-diamine four (methylene phosphonic acid) blend (HMDTA), to reduce the fouling that is higher than lime carbonate in 9 the Black Liquid Evaporator system at pH.This patent is also open, adopts single phosphonic acid ester, rather than disclosed blend, and is then invalid for be higher than under 9 the condition inhibition calcium carbonate crystal in pH value.
United States Patent (USP) 4,851,490 (authorize people such as Fu Chen, 1989-07-25) a kind of water-soluble polymers of hydroxyl alkylidene amino alkylidene group phosphate functional degree is disclosed, allegedly can be used as deposition control agent, system is all effective as cooling, boiler, conversion coating, paper and slurrying processing and gas drip washing etc. to various water bodies.
United States Patent (USP) 5,534,157 (authorize people such as Craig D.Iman, 1996-07-09) disclose a kind of polyether polyamine methene phosphonate ester that adopts and suppress scaling salt formation, deposition and adherent method in high pH process water.At the row 4 of its specification sheets, in the row 35～51, this patent disclosure, inhibitor such as HEDP and ATMP are useless under the alkaline pH condition as fouling inhibitor.
United States Patent (USP) 5,562,830 (authorize people such as Davor F.Zidovec, 1996-10-08) disclose a kind of corrosion and fouling and sedimentary method that suppresses aqueous systems by the combination that adds many Epoxysuccinic acids or its salt and phosphono carboxylic acid or its salt.
United States Patent (USP) 5,552,018 (authorizes Johan Devenyns, 1996-09-03) a kind of method is disclosed, wherein improve through the delignification in the presence of chemical reagent and handle with peroxy acid, for example, the delignification selectivity of the dissolving pulp after the kraft cooking.Disclose with phosphoric acid ester as the stablizer in this method.
Although patent recited above and technical article are arranged, still press at present and be used to suppress dirt, particularly the generation in the technical chemistry pulping process equipment, deposition and adherent modification method and composition in the metallic surface.
Summary of the invention
The purpose of this invention is to provide a kind of calcium salt dirt formation on metal and other surfaces, deposition and adherent composition in equipment, container and/or the pipeline of chemical pulping process facility of suppressing.Another object of the present invention provides a kind of calcium salt dirt formation on the various surfaces, deposition and adherent method in equipment, container and/or the pipeline of chemical pulping process facility of suppressing.
These and other purpose can be realized by the present invention, yet the description of following relevant details of the present invention is an indefiniteness.
According to the present invention, a kind of dirt composite inhibiting of calcium salt in the alkaline aqueous mixture fouling of chemical pulping process that be used for suppressing is provided, wherein said composition is added in the black liquor of chemical pulping process, said composition contains at least a phosphonic acid ester of effective scale suppression consumption, is selected from the compound of following general formula:
M 2O 3P-CH 2-N(R 1)-(CH 2) m-N(R 2)-CH 2PO 3M 2???????(I)
The compound of following general formula:
R 3-C(OH)(PO 3M 2) 2????????????????????????????(II)
The compound of following general formula:
N-(CH 2PO 3M 2) 3???????????????????????????????(III)
The phosphonic acid ester of following general formula:
Figure A0281550200151
The general formula (I) and (III) amine oxide of phosphonic acid ester,
Or its mixture, wherein M is independently selected from hydrogen, basic metal, alkaline-earth metal or ammonium, R 1And R 2Be independently selected from CH 2PO 3M 2Or (CH 2) n-N-(CH 2PO 3M 2) 2, m is 2 or 3, n is 2 or 3, R 3Be the alkyl group and the R of 1～17 carbon atom 3Be optional branching and optional undersaturated, condition is:
(a) this phosphonic acid ester is not the blend of general formula (II) phosphonic acid ester and general formula (III) phosphonic acid ester,
(b) this phosphonic acid ester is not general formula (II) phosphonic acid ester and general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2The blend of phosphonic acid ester,
(c) be selected from phosphonic acid ester, the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester or general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, said composition does not contain nonionogenic tenside,
(d) be selected from the phosphonic acid ester or the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, this phosphonic acid ester greater than 25ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid, and
(e) when this phosphonic acid ester is selected from the phosphonic acid ester of general formula (IV), this phosphonic acid ester greater than 20ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid.
And then, according to the present invention, provide a kind of method that suppresses calcium salt scale in the chemical pulping process, comprising: effectively the above-mentioned composition of scale suppression consumption carries out blending with the black liquor that reclaims from pulp digester.
Detailed Description Of The Invention
First embodiment of the invention relates to a kind of scale suppression composition, be used for suppressing the formation of the alkaline aqueous mixture calcium salt dirt of chemical pulping process, wherein said composition is added in the black liquor of chemical pulping process, said composition comprises at least a phosphonic acid ester of effective scale suppression consumption, is selected from the compound of following general formula:
M 2O 3P-CH 2-N(R 1)-(CH 2) m-N(R 2)-CH 2PO 3M 2????????(I)
The compound of following general formula:
R 3-C(OH)(PO 3M 2) 2?????????????????????????????(II)
The compound of following general formula:
N-(CH 2PO 3M 2) 3????????????????????????????????(III)
The phosphonic acid ester of following general formula:
Figure A0281550200161
The general formula (I) and (III) amine oxide of phosphonic acid ester,
Or its mixture, wherein M is independently selected from hydrogen, basic metal, alkaline-earth metal or ammonium, R 1And R 2Can be identical or different, and be independently selected from-CH 2PO 3M 2Or-(CH 2) n-N-(CH 2PO 3M 2) 2, m is 2 or 3, n is 2 or 3, R 3Be the alkyl group and the R of 1～17 carbon atom 3Be optional branching and optional undersaturated, condition is:
(a) this phosphonic acid ester is not the blend of general formula (II) phosphonic acid ester and general formula (III) phosphonic acid ester,
(b) this phosphonic acid ester is not general formula (II) phosphonic acid ester and general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2The blend of phosphonic acid ester,
(c) be selected from phosphonic acid ester, the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester or general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, said composition does not contain nonionogenic tenside,
(d) be selected from the phosphonic acid ester or the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, this phosphonic acid ester greater than 25ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid, and
(e) when this phosphonic acid ester is selected from the phosphonic acid ester of general formula (IV), this phosphonic acid ester greater than 20ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid.
In phosphonic acid ester of the present invention, M is hydrogen or basic metal preferably, and this basic metal is sodium and potassium preferably, R 3The alkyl group of 1～5 carbon atom preferably, more preferably methyl, and m preferably 2.
Scale suppression composition of the present invention includes but not limited to, at least a general formula (I) phosphonic acid ester, at least a general formula (II) phosphonic acid ester, at least a general formula (III) phosphonic acid ester, at least a general formula (IV) phosphonic acid ester, at least a general formula (I) or (III) amine oxide of phosphonic acid ester, the mixture of at least two kinds of general formulas (I) phosphonic acid ester, at least a general formula (I) phosphonic acid ester and at least a general formula (II), the mixture of general formula (III) or general formula (IV) phosphonic acid ester, the mixture of at least two kinds of general formulas (II) phosphonic acid ester, perhaps at least a general formula (I) or (III) amine oxide of phosphonic acid ester and at least a general formula (I) or (III) mixture of phosphonic acid ester.Preferably, the mixture of the mixture of the phosphonic acid ester that scale suppression composition of the present invention is at least a general formula (I), at least two kinds of general formulas (I) phosphonic acid ester, at least a general formula (I) phosphonic acid ester and at least a general formula (II) or general formula (III) phosphonic acid ester, the mixture of perhaps at least a general formula (II) phosphonic acid ester and at least a general formula (IV) phosphonic acid ester.
The example of suitable phosphonic acid ester includes but not limited to, the phosphonic acid ester in the following table 1.Following table 1 provides the molecular formula of general formula (I), (II) and representative phosphonic acid ester (III).The phosphonic acid ester of table 1 is by Solutia company, 575 maryvi1le Centre Drive, and St.Louis, MO is with the supply of trade(brand)name Dequest  phosphonic acid ester and with its Dequest  phosphonic acid ester production number identification.
Table 1
Production number Molecular formula ?R 1 R 2 m n R 3 M
?2000 ?III ?--- --- --- --- --- 6H
?2006 ?III ?--- --- --- --- --- 5Na，1H
?2010 ?II ?--- --- --- --- CH 3 4H
?2016 ?II ?--- --- --- --- CH 3 4Na
?2041 ?I ?CH 2PO 3M 2 CH 2PO 3M 2 2 --- --- 8H
?2046 ?I ?CH 2PO 3M 2 CH 2PO 3M 2 2 --- --- 3H，5Na
?2060 ?I ?CH 2PO 3M 2 (CH 2) nN(CH 2PO 3M 2) 2 2 2 --- 10H
?2066 ?I ?CH 2PO 3M 2 (CH 2) nN(CH 2PO 3M 2) 2 2 2 --- 7Na，3H
?7000 ?IV ?--- --- --- --- --- 5H
The molecular formula and the corresponding title of the listed Dequest  of table 1 phosphonic acid ester are as shown below.
Dequest 2000-amino-three (methylene phosphonic acid)
N(CH 2PO 3H 2) 3
Dequest 2006-amino-three (methylene phosphonic acid) sodium salt
Na 5H[N(CH 2PO 3) 3]
Dequest 2010-1-hydroxy ethylidene (1, the 1-di 2 ethylhexyl phosphonic acid)
CH 3C(OH)(PO 3H 2) 2
Dequest 2016-1-hydroxy ethylidene (1, the 1-di 2 ethylhexyl phosphonic acid) sodium salt
Na 4[CH 3C(OH)(PO 3) 2]
Dequest 2041-ethylene diamine four (methylene phosphonic acid)
H 8[(O 3PCH 2) 2NCH 2CH 2N(CH 2PO 3) 2]
Dequest 2046-ethylene diamine four (methylene phosphonic acid), five sodium-salt
Na 5H 3[(O 3PCH 2) 2NCH 2CH 2N(CH 2PO 3) 2]
Dequest 2054-[1,6-hexylidene two [nitrilo two (methylene radical)]] four-phosphonic acids, sylvite
K 6H 2[(O 3PCH 2) 2N(CH 2) 6N(CH 2PO 3) 2]
Dequest 2060-diethylenetriamine-five (methylene phosphonic acid)
(H 2O 3PCH 2) 2NCH 2CH 2N(CH 2PO 3H 2)CH 2CH 2N(CH 2PO 3H 2) 2
Dequest 2066-diethylenetriamine-five (methylene phosphonic acid) sodium salt
Na 7H 3[O 3PCH 2] 2NCH 2CH 2N(CH 2PO 3)CH 2CH 2N(CH 2PO 3) 2]
Dequest 7000-2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid
The phosphonic acid ester of another kind of preferred general formula (I) is a compound N, N '-two (3-aminopropyl) ethylene diamine-six (methylene phosphonic acid) or its salt, and wherein this salt is salt such as sodium, potassium, ammonium.When this compound was sodium salt, compound had general formula
Na xH y[(O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3) CH 2CH 2N (CH 2PO 3) CH 2CH 2CH 2N-(CH 2PO 3) 2]; Wherein x+y is 12, and here note is 4NHMP.This compound can be according to United States Patent (USP) 5,261,491, and is for referencial use in these receipts, in example 1 disclosed program preparation.
The phosphonic acid ester of preferred general formula (I) is
(M 2O 3PCH 2) 2NCH 2CH 2N(CH 2PO 3M 2) 2，
(M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, or
(M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2, more preferably (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2Or
(M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2, most preferably
(M 2O 3PCH 2) 2NCH 2CH 2CH 2N(CH 2PO 3M 2)CH 2CH 2N(CH 2PO 3M 2)CH 2CH 2CH 2N-(CH 2PO 3M 2) 2。
The phosphonic acid ester of preferred general formula (II) is H 3C-C (OH) (PO 3M 2) 2, more preferably H 3C-C (OH) (PO 3Na 2) 2
At least two kinds be independently selected from general formula (I), (II), (III) and (IV) phosphonic acid ester phosphonic acid ester and general formula (I) and (III) the amine oxide blend of phosphonic acid ester can use according to the present invention.The preferred at present blend that uses two kinds of phosphonic acid esters, the blend of its formula of (I) phosphonic acid ester and general formula (I), general formula (II), general formula (III) or general formula (IV) phosphonic acid ester is preferred, and the blend of the phosphonic acid ester of two kinds of general formulas (I) is most preferred.The composition of blend can change in wide region, and wherein the percentage of every kind of component changes in 1～99% wide region, as long as every kind of phosphonic acid ester exists with the consumption at least about 1wt%.Preferably, every kind of phosphonic acid ester exists with the consumption at least about 10wt%.Under the situation of the blend of two kinds of components, every kind of phosphonic acid ester is preferably with about 10～about 90wt%, and more preferably the consumption with about 20～about 80wt% exists.
Being preferred for blend of the present invention is to be selected from N, the phosphonic acid ester of N '-two (3-aminopropyl) ethylene diamine-six (methylene phosphonic acid), diethylenetriamine-five (methylene phosphonic acid) or its salt, with the blend that is selected from general formula (I), (II), (III) or phosphonic acid ester (IV), perhaps be selected from phosphonic acid ester or its salt and the phosphonic acid ester blend that is selected from general formula (I) or phosphonic acid ester (III) of ethylene diamine four (methylene phosphonic acid).Preferred phosphonic acid ester blend is to be selected from N, phosphonic acid ester or its salt of N '-two (3-aminopropyl) ethylene diamine-six (methylene phosphonic acid), ethylene diamine four (methylene phosphonic acid), diethylenetriamine-five (methylene phosphonic acid), blend with the another kind of phosphonic acid ester that is selected from general formula (I) phosphonic acid ester, and be selected from N, the phosphonic acid ester of N '-two (3-aminopropyl) ethylene diamine-six (methylene phosphonic acid), diethylenetriamine-five (methylene phosphonic acid) or its salt and the phosphonic acid ester blend that is selected from general formula (II) phosphonic acid ester.
The phosphonic acid ester of effective level or phosphonic acid ester blend are used for the manufacturing of scale suppression composition of the present invention and use.This effective level depends on employed concrete phosphonic acid ester and other factors among the present invention of implementing, include but not limited to, the operational condition of pulp digester composition, pulp digester (promptly, the H-coefficient), the black liquor composition, and operational condition and other factors well known by persons skilled in the art and the condition of pulp washing operation and black liquor recovery operation before floating.The those skilled in the art that are chosen in of phosphonic acid ester effective level have studied carefully and will understand after this specification sheets.
When scale suppression composition of the present invention was at least a general formula (I) phosphonic acid ester, effective scale suppression consumption of this phosphonic acid ester and every kind was as follows.
When using in this article, the ppm consumption level of fouling inhibitor is a benchmark with the total soup weight that adds, and the density of wherein supposing soup is 1g/mL.
When phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2The time, be about 10～about 1000ppm by the phosphonic acid ester effective level of active acid, preferred about 20～about 500ppm, more preferably from about 30～500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The time, be about 30～about 1000ppm by the phosphonic acid ester effective level of active acid, preferred about 40～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2The time, be about 10～about 1000ppm by the phosphonic acid ester effective level of active acid, preferred about 20～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When scale suppression composition of the present invention was the phosphonic acid ester of at least a general formula (II), this phosphonic acid ester is CH preferably 3C (OH) (PO 3M 2) 2, and be about 20～about 200ppm by the effective scale suppression consumption of the phosphonic acid ester of active acid, preferred about 30～about 100ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When scale suppression composition of the present invention is the phosphonic acid ester of at least a general formula (III), be about 50～about 1000ppm by the effective scale suppression consumption of the phosphonic acid ester of active acid, preferred about 80～about 500ppm is a benchmark with the black liquor weight that reclaims from pulp digester.
When scale suppression composition of the present invention is the phosphonic acid ester of at least a general formula (IV), be about 50～about 500ppm by the effective scale suppression consumption of the phosphonic acid ester of active acid, preferred about 100～about 200ppm is a benchmark with the black liquor weight that reclaims from pulp digester.
When scale suppression composition of the present invention was the amine oxide of at least a general formula (I) or general formula (III) phosphonic acid ester, this amine oxide was by the effective scale suppression consumption of active acid and the effective level equivalent of corresponding general formula (I) or general formula (III) phosphonic acid ester.
When scale suppression composition of the present invention was the mixture of the mixture of at least two kinds of general formulas (I) phosphonic acid ester or at least a general formula (I) phosphonic acid ester and at least a general formula (III) phosphonic acid ester, effective scale suppression consumption of this phosphonic acid ester and every kind was as follows.
When first phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2-N (CH 2PO 3M 2) 2The time, second phosphonic acid ester preferably is selected from N (CH 2PO 3M 2) 3, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2When second phosphonic acid ester is N (CH 2PO 3M 2) 3The time, be about 10～about 1000ppm by the amount of mixture of active acid, preferred about 200～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.When second phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2The time, be about 20～about 1000ppm by the amount of mixture of active acid, preferred about 30～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.When second phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The time, be about 10～about 1000ppm by the amount of mixture of active acid, preferred about 30～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When first phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2The time, second phosphonic acid ester preferably is selected from (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Or N (CH 2PO 3M 2) 3When second phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The time, be about 20～about 1000ppm by the amount of mixture of active acid, preferred about 40～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.When second phosphonic acid ester is N (CH 2PO 3M 2) 3The time, be about 30～about 1000ppm by the amount of mixture of active acid, preferred about 50～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
When first phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2And second phosphonic acid ester is N (CH 2PO 3M 2) 3The time, be about 50～about 1000ppm by the amount of mixture of active acid, preferred about 150～about 500ppm is a benchmark with the black liquor weight from the pulp digester recovery.
The preferred blends of at least two kinds of general formula (I) phosphonic acid esters or at least a general formula (I) phosphonic acid ester and at least a general formula (III) phosphonic acid ester is the blend of following phosphonic acid ester: (M 2O 3PCH 2) 2NCH 2CH 2CH 2H (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2-N (CH 2PO 3M 2) 2With N (CH 2PO 3M 2) 3, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2With (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, or N (CH 2PO 3M 2) 3Blend.
The most preferably blend of at least two kinds of general formula (I) phosphonic acid esters or at least a general formula (I) phosphonic acid ester and at least a general formula (III) phosphonic acid ester is the blend of following phosphonic acid ester:
(M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2)-CH 2CH 2CH 2N (CH 2PO 3M 2) 2With N (CH 2PO 3M 2) 3, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Blend.
When scale suppression composition of the present invention was the mixture of phosphonic acid ester of the phosphonic acid ester of at least a general formula (I) and at least a general formula (II), effective scale suppression consumption of this phosphonic acid ester and every kind was as follows.
Preferred blends is to be selected from (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2Or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, first phosphonic acid ester be selected from CH 3C (OH) (PO 3M 2) 2The mixture of second phosphonic acid ester.
When first phosphonic acid ester is selected from (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2The time, be about 10～about 500ppm by the amount of mixture of active acid, preferred about 30～about 150ppm is a benchmark with the black liquor weight from the pulp digester recovery.When first phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The time, be about 30～about 1000ppm by the amount of mixture of active acid, preferred about 50～about 200ppm is a benchmark with the black liquor weight from the pulp digester recovery.
The most preferably blend of at least a general formula (I) phosphonic acid ester and at least a general formula (II) phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N-(CH 2PO 3M 2) 2With CH 3C (OH) (PO 3M 2) 2Blend.
Second embodiment of the invention relates to the method that suppresses calcium salt scale in the alkali electroless pulping process, comprise: at least a phosphonic acid ester that in the black liquor of chemical pulping process, adds effective scale suppression consumption, wherein said composition comprises at least a phosphonic acid ester, is selected from the compound of following general formula:
M 2O 3P-CH 2-N(R 1)-(CH 2) m-N(R 2)-CH 2PO 3M 2???????????(I)
The compound of following general formula:
R 3-C(OH)(PO 3M 2) 2????????????????????????????????(II)
The compound of following general formula:
N-(CH 2PO 3M 2) 3???????????????????????????????????(III)
The phosphonic acid ester of following general formula:
Figure A0281550200231
The general formula (I) and (III) amine oxide of phosphonic acid ester,
Or its mixture, wherein M is independently selected from hydrogen, basic metal, alkaline-earth metal or ammonium, R 1And R 2Be independently selected from-CH 2PO 3M 2Or-(CH 2) n-N-(CH 2PO 3M 2) 2, m is 2 or 3, n is 2 or 3, R 3Be the alkyl group and the R of 1～17 carbon atom 3Be optional branching and optional undersaturated, condition is:
(a) this phosphonic acid ester is not the blend of general formula (II) phosphonic acid ester and general formula (III) phosphonic acid ester,
(b) this phosphonic acid ester is not general formula (II) phosphonic acid ester and general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2The blend of phosphonic acid ester,
(c) be selected from phosphonic acid ester, the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester or general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, said composition does not contain nonionogenic tenside,
(d) be selected from the phosphonic acid ester or the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, this phosphonic acid ester greater than 25ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid, and
(e) when this phosphonic acid ester is selected from the phosphonic acid ester of general formula (IV), this phosphonic acid ester greater than 20ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid.
The inventive method is at chemical pulping process, for example in the enforcement of sulphate process, and moisture phosphonate compositions of the present invention and the black liquor blending of reclaiming from pulp digester.The moisture phosphonate compositions of the present invention can adopt any conventional apparatus well known by persons skilled in the art to join in the black liquor.In addition, the moisture phosphonate compositions of the present invention can promptly before the Black Liquid Evaporator, directly join in the black liquor in black liquor recovery before the stage, and perhaps it can promptly join in the black liquor between each effect of MEE during the black liquor recovery stage.Which effect is representative temperature scope in the Black Liquid Evaporator generally between about 80～about 180 ℃, depend on.The pH value of the black liquor in the alkali electroless pulping process is 9 at least.Under the situation of sulphate process, the pH value of black liquor preferably between about 10～about 14, more preferably from about 12～about 14.The moisture phosphonate compositions of the present invention can join in the black liquor by any traditional way well known by persons skilled in the art.For example, in the batch digester operation, the adding of the moisture phosphonate compositions of the present invention can add at the beginning or during the Black Liquid Evaporator cycle by the gross in the black liquor recovery stage, and perhaps it can divide many batches to add or add continuously from start to finish with black liquor recovery along the Black Liquid Evaporator cycle.At present preferably with the moisture phosphonate compositions of the present invention with the form of material by the gross or add when beginning near the Black Liquid Evaporator cycle.Under the situation of continuous steamer operation, the moisture phosphonate compositions of the present invention joins in the black liquor serially, keep the effective concentration of phosphonic acid ester in black liquor whereby, if perhaps black liquor was stored in before the stage in the storage tank in Black Liquid Evaporator, then it can be by top described adding.
The consumption of scale suppression composition of the present invention is the effective level that is enough to provide effective scale suppression phosphonic acid ester concentration in Black Liquid Evaporator, should make its action time in the black liquor recovery operation, and in addition formation, deposition and the adhesion of the calcium salt dirt, particularly lime carbonate in pulp digester and/or brown stock washers and the calcium sulfate dirt inhibition of being satisfied with.Use acceptable calcium salt dirt level in pulp digester, brown stock washers and the black liquor recovery operation that one skilled in the art will know that concrete chemical pulping facility of the present invention, and be easy to select appropriate phosphonic acid ester and concentration to join in the black liquor, require and the time length with the scale suppression that reaches according to this specification sheets regulation.Those skilled in the art will be very clear after having studied this specification sheets carefully, and many type factors mentioned in this article and other factors will determine to realizing that this scale suppression requires needed phosphonic acid ester consumption of the present invention.Consider the direction that this paper provided, determining of this kind consumption is that those skilled in the art are competent at, and do not need unnecessary experiment.
The 3rd embodiment of the present invention relates to the method that suppresses calcium salt scale in the Aquo System in the alkaline pulp-making method of selecting, comprise: determine that (a) the calcium salt dirt that phosphonic acid ester concentration and technological temperature changed with phosphate-ester composition and the black liquor composition blending time of reclaiming from the chemical pulping process pulp digester suppresses curve, (b) determine that the needed calcium salt dirt of the chemical pulping process of selecting suppresses ability, wherein should be according to the time, process conditions such as temperature and pressure and black liquor are formed to determine, (c) and (b) according to step (a), select the fouling of calcium salt the chemical pulping process that appropriate phosphate-ester composition and phosphonic acid ester working concentration suppress to select with from black liquor composition blending that the chemical pulping process pulp digester reclaims the time with convenient phosphonic acid ester effectively, and (d) the black liquor composition in the alkali electroless pulping process of the phosphate-ester composition selected and selection is carried out blending in the black liquor recovery stage of chemical pulping process; Wherein the phosphate-ester composition of Xuan Zeing according to top about regulation of the present invention.
The 4th embodiment of the present invention relates to the method that suppresses calcium salt scale in the Aquo System in the alkali electroless pulping process of selecting, comprise: (a) according to the time, process conditions and the desired calcium salt dirt inhibition of the definite chemical pulping process of selecting of black liquor composition abilities such as temperature and pressure, (b) select appropriate phosphate-ester composition and phosphonic acid ester working concentration, the fouling of calcium salt in the chemical pulping process that the chemical pulping process of selecting, suppresses effectively to select during blending with convenient phosphonic acid ester and the black liquor composition that reclaims from pulp digester, wherein should suppress curve and determine, and (c) phosphate-ester composition of selecting and the black liquor composition that reclaims are carried out blending during the boiling stage of chemical pulping process from the chemical pulping process pulp digester of selecting according to the calcium salt dirt that step (a) and phosphonic acid ester concentration and technological temperature changed with phosphate-ester composition and the black liquor composition blending time of reclaiming from the chemical pulping process pulp digester; Wherein the phosphate-ester composition of Xuan Zeing according to top about regulation of the present invention.
In the present invention's third and fourth embodiment, the calcium salt dirt that phosphonic acid ester concentration and technological temperature changed with phosphate-ester composition and the black liquor composition blending time of reclaiming from the chemical pulping process pulp digester suppresses curve, can be by carrying out laboratory experiment, for example, described herein, perhaps determine by carrying out fairly large test.Will be as each chemical pulping process along with institute's converted timber type, the concrete operational condition that adopts, black liquor are formed, composition in the pulp digester and the variation, concrete phosphonic acid ester or phosphonic acid ester blend and be that the concentration that meets the requirements of the required use of scale suppression effect will depend on concrete chemical pulping process.Utilize the calcium salt dirt to suppress curve, cooperate selected chemical pulping process again, mainly refer to operational conditions such as its time, temperature and pressure, black liquor is formed and the desired calcium salt dirt of moisture pulp digester composition suppresses ability, the fouling of calcium salt in the chemical pulping process that those skilled in the art will suppress to select in the time of can selecting appropriate phosphate-ester composition and phosphonic acid ester working concentration with the black liquor composition blending in the chemical pulping process of convenient phosphonic acid ester and selection effectively.
The present invention will utilize the following examples to be described further, but these embodiment do not intend limiting the present invention.Unless point out separately, all consumptions and percentage ratio refer to weight without exception.
Embodiment
In the following embodiments, with using the calcium salt scale test of carrying out at from the black liquor that is positioned at Middle West-obtain, so as to illustrating the application of the present composition in the inventive method by the tame sulfate pulp-making factory in north.In the process of implementing these tests, gather the black liquor composition sample at the select time of process of the test.Total calcium adopts the analysis of AtomicAbsorption Spectroscopy (AA) (atomic absorption spectroscopy) to determine with the concentration that is suppressed calcium.Being suppressed calcium is can be by the calcium amount of 0.45 μ m strainer.Test will be carried out in accordance with the general procedure that describes below.In addition, test at the phosphonate compositions of every kind of test, is that the selected inhibitor concentration of benchmark and the situation that does not have inhibitor are implemented at 100ppm by active acid, with the black liquor amount generally normally.
The black liquor test
Here employed black liquor test is developed and is used for measuring the scale suppression performance of the present composition in the black liquor composition.The temperature of black liquor composition is slowly climbed 150 ℃ from room temperature in about 45min～1h, keep 1～2h at 150 ℃ subsequently.Sample adopts the extractor of liquid cooling to take out from the condensation pipe of Pa Er bullet (Parr Bomb) reactor under the various different times of duration of test interval, pressure and temperature, so that adopt the atomic absorption detecting sequential monitoring calcium concn that describes below.
The charging program and the test conditions of Pa Er bullet reactor
Rare black liquor sample (about 15wt% solid), the Black Liquid Evaporator of the sulfate process of Miao Shuing is before from the sampling spot collection in the above.
The phosphonic acid ester charging of being adopted is by active acid, is that benchmark is represented with the black liquor weight that joins in the Pa Er bullet reactor.The employed concentration level by active acid of this paper is the pure free acid consumption (ppm) with the concrete phosphonic acid ester actual dose equivalent that uses.
The preparation of black liquor sample
Rare black liquor that about 1.5L obtains from above is transferred in the 2L capacity flask.
In Comparative Examples, in the black liquor unconstrained dose.In the test of sample of the present invention, the inhibitor that is enough to reach requirement concentration in 2L is added in the flask in the material, adds rare black liquor then to fill with the scale to 2L.
The charging of Pa Er bullet reactor and the monitoring of calcium release test
Prepare black liquor according to top program.
Before each on-test, Pa Er bullet reactor carries out pickling with 10% sulfuric acid, to remove any existing settling.After the pickling, pulp digester is with washed with de-ionized water.
The black liquor (1.5L) that contains or do not contain inhibitor is transferred in the Pa Er bullet reactor (2L), and the start-of-record temperature.The extractor pipeline is got the 5mL sample then and is carried out the AA analysis with purging with nitrogen gas.Start heating sequence and writing time t=0.Heating sequence is that Pa Er bullet reactor content is heated to 150 ℃ from room temperature in 1h, and keeps 150 ℃ temperature (about 1～2h) in all the other times of test.
(it is to adopt Perkin Elmer 100 type spectrometers to implement by atomic absorption according to flame spectrometry that AA analyzes; General Principle can be referring to " instrument analytical method " Hobart H.Willard, Lynn L.Merritt, Jr.; John A Dean, the 4th edition, D.Van Nostrand company, 1965-08)
Quantitative 1mL sample transfer is in the centrifuge tube that 5mL4%HCl solution is housed and adopt AA to determine the calcium contents of sample, promptly total calcium.All the other samples are drawn in the 10mL syringe and by 0.45 μ m syringe filter and filter.Quantitative 1mL filtrate is transferred in the centrifuge tube that 5mL4%HCl solution is housed and is adopted AA to determine the calcium contents of filtrate, promptly is suppressed calcium.
During whole test, during for example about 2～3h, remove the soup in the condensation pipe one time every 10min, carry out temperature measuring, and extract about 5mL soup sample out.Repeat above-described AA routine analyzer subsequently.After off-test, calcium contents and temperature data were marked and drawed the time.
Each following example all carries out according to the general procedure that provides above.All concentration levels are all to provide by the phosphonic acid ester ppm value of active acid with respect to black liquor weight.
The phosphonic acid ester that uses in the example is that (St.Louis MO) obtains from Solutia company.Except this paper regulation, the chemical that uses in the example all obtains from Fisher Scientific company.
Table 3～7 that begin from below to provide provide the data that obtain from the black liquor of the various different phosphonic acid esters of a series of employings.The phosphonic acid ester of being tested marks in the title of every form below with name of product (as the table 1 here and 2 defineds).Temperature is degree centigrade being unit.The ppm of calcium is based on the umber of each 1,000,000 parts of soup weight.
Example 1
Reception test in the test that unconstrained dose black liquor sample (Comparative Examples) is described in example one joint.The result is stated from following table 3.
Table 3-Comparative Examples-unconstrained dose
Time, min Total calcium, ppm Be suppressed calcium, ppm Temperature
????0 ????34.4 ????28 ????19
????10 ????34.6 ????27 ????23
????20 ????35 ????28.1 ????55
????30 ????36.3 ????27.7 ????78
????40 ????33.7 ????28.6 ????99
????50 ????35.6 ????28.4 ????121
????60 ????34.1 ????21.7 ????140
????75 ????32 ????4.5 ????151
????90 ????30.8 ????2.6 ????150
????105 ????31.5 ????1.6 ????150
????120 ????29.8 ????0.6 ????150
Example 2
Accepted test with the concentration of 100ppm active acid in the test that Dequest 2006 describes in example one joint.The result is stated from following table 4.
Table 4-100ppm Dequest 2006
Time, min Total calcium, ppm Be suppressed calcium, ppm Temperature
????0 ????25 ????22.6 ????19
????30 ????25.2 ????24.5 ????103
????40 ????25.1 ????23.6 ????134
????50 ????26.3 ????22.5 ????150
????60 ????26.3 ????22.8 ????150
????70 ????26.3 ????22.1 ????150
????80 ????26.2 ????19.7 ????150
????90 ????26.3 ????18.2 ????150
????105 ????26.2 ????12.6 ????150
????120 ????23.6 ????8.6 ????150
The data of this example show, the working concentration of 100ppm with do not use inhibitor to compare to provide the calcium of remarkable improvement to suppress effect.The data of this example show that Dequest 2000 and Dequest 2006 will suppress calcium salt scale effectively according to the present invention.
Example 3
Accepted test with the concentration of 100ppm active acid in the test that Dequest 2016 describes in example one joint.The result is stated from following table 5.
Table 5-100ppm Dequest 2016
Time, min Total calcium, ppm Be suppressed calcium, ppm Temperature
????0 ????34.2 ????28.9 ????20
????10 ????34.9 ????27.5 ????37
????20 ????34.7 ????29.2 ????79
????30 ????36.8 ????27.7 ????120
????40 ????36.2 ????28.6 ????148
????50 ????37.2 ????26.3 ????150
????60 ????35.5 ????25.4 ????149
????70 ????36 ????25.4 ????150
????80 ????34.4 ????25.6 ????150
????90 ????34.9 ????24.4 ????150
????105 ????36.2 ????23.6 ????150
????120 ????33.9 ????22.9 ????150
The data of this example show, the working concentration of 100ppm with do not use inhibitor to compare to provide the calcium of remarkable improvement to suppress effect.The data of this example show that Dequest 2010 and Dequest 2016 will suppress calcium salt scale effectively according to the present invention.
Example 4
In the test that Dequest 2066 describes in example one joint with 10 and the concentration of 100ppm active acid accepted test.The result is stated from following table 6 and 7.
Table 6-100ppm Dequest 2066
Time, min Total calcium, ppm Be suppressed calcium, ppm Temperature
????0 ????25.7 ????25.8 ????19
????10 ????26.2 ????25.9 ????31
????20 ????27.1 ????26.1 ????69
????30 ????26.3 ????25.2 ????112
????40 ????26.9 ????22.4 ????134
????50 ????24.5 ????23 ????150
????60 ????26 ????22.7 ????150
????70 ????26.9 ????23.1 ????150
????80 ????27.1 ????23.5 ????150
????90 ????23.5 ????22.5 ????150
????105 ????26.1 ????23.1 ????150
????120 ????26 ????22.8 ????150
Table 7-10ppm Dequest 2066
Time, min Total calcium, ppm Be suppressed calcium, ppm Temperature
????0 ????22.5 ????21.5 ????49
????15 ????23.1 ????21.3 ????101
????30 ????23 ????21.5 ????132
????40 ????23.5 ????22.1 ????150
????50 ????23.3 ????21.2 ????150
????60 ????22.9 ????18.5 ????150
????70 ????22.9 ????14.4 ????150
????80 ????23.2 ????9.4 ????150
????90 ????22.8 ????6.5 ????150
????105 ????23.2 ????4.2 ????150
????120 ????22.4 ????2.8 ????150
The data of this example show that the working concentration of 100ppm suppresses effect with not using inhibitor or use the 10ppm inhibitor to compare the calcium that remarkable improvement is provided.The data of this example show that Dequest 2060 and Dequest 2066 adopt the concentration level of about 40ppm～about 500ppm to suppress calcium salt scale effectively according to the present invention.
Above description is intended to illustrate, and should not be considered as restrictive.Various modification and replacement scheme are easy to associate In the view of those skilled in the art.Therefore be intended that, above description should be only as example, and scope of the present invention is by following claim regulation.What also will declare is, every claim define with regard to speech meaning speech should be considered as comprising any and all and here the content clearly stipulated of literal there is no the conversion scheme of substantive difference, but except the conversion scheme of the prior art.

Claims (79)

1. one kind is used for suppressing the dirt composite inhibiting of calcium salt in the alkaline aqueous mixture fouling of chemical pulping process, wherein said composition is added in the black liquor of chemical pulping process, described composition contains at least a phosphonic acid ester of effective scale suppression consumption, is selected from the compound of following general formula:
M 2O 3P-CH 2-N(R 1)-(CH 2) m-N(R 2)-CH 2PO 3M 2???????????(I)
The compound of following general formula:
R 3-C(OH)(PO 3M 2) 2????????????????????????????????(II)
The compound of following general formula:
N-(CH 2PO 3M 2) 3???????????????????????????????????(III)
The phosphonic acid ester of following general formula:
Figure A028155020002C1
The general formula (I) and (III) amine oxide of phosphonic acid ester,
Or its mixture, wherein M is independently selected from hydrogen, basic metal, alkaline-earth metal or ammonium, R 1And R 2Be independently selected from-CH 2PO 3M 2Or-(CH 2) n-N-(CH 2PO 3M 2) 2, m is 2 or 3, n is 2 or 3, R 3Be the alkyl group and the R of 1～17 carbon atom 3Be optional branching and optional undersaturated, condition is:
(a) this phosphonic acid ester is not the blend of general formula (II) phosphonic acid ester and general formula (III) phosphonic acid ester,
(b) this phosphonic acid ester is not general formula (II) phosphonic acid ester and general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2The blend of phosphonic acid ester, (c) be selected from phosphonic acid ester, the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester or general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, said composition does not contain nonionogenic tenside,
(d) be selected from the phosphonic acid ester or the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, this phosphonic acid ester greater than 25ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid, and
(e) when this phosphonic acid ester is selected from the phosphonic acid ester of general formula (IV), this phosphonic acid ester greater than 20ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid.
2. the composition of claim 1, wherein M is independently selected from hydrogen or basic metal.
3. the composition of claim 2, wherein when M was basic metal, M was sodium or potassium.
4. the composition of claim 1, wherein R 1And R 2Be CH 2PO 3M 2
5. the composition of claim 4, wherein m is 2.
6. the composition of claim 1, wherein R 1And R 2Be (CH 2) n-N-(CH 2PO 3M 2) 2
7. the composition of claim 6, wherein m is 2, n is 3.
8. the composition of claim 1, wherein R 1Be CH 2PO 3M 2And R 2Be (CH 2) n-N-(CH 2PO 3M 2) 2
9. the composition of claim 8, wherein m is 2, n is 2.
10. the composition of claim 1, wherein R 3It is the alkyl group of 1～5 carbon atom.
11. the composition of claim 10, wherein R 3It is methyl.
12. the composition of claim 1, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (I).
13. the composition of claim 1, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (II).
14. the composition of claim 1, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (III).
15. the composition of claim 1, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (IV).
16. the composition of claim 1, wherein said phosphonic acid ester are at least a general formula (I) and (III) amine oxide of phosphonic acid ester.
17. the composition of claim 1, wherein said phosphonic acid ester are the mixtures of at least two kinds of general formulas (I) phosphonic acid ester.
18. the composition of claim 1, wherein said phosphonic acid ester are the mixtures of at least a general formula (I) phosphonic acid ester and at least a general formula (II) phosphonic acid ester.
19. the composition of claim 1, wherein said phosphonic acid ester are the mixtures of at least a general formula (I) phosphonic acid ester and at least a general formula (III) phosphonic acid ester.
20. the composition of claim 1, wherein said phosphonic acid ester are the mixtures of at least two kinds of general formulas (II) phosphonic acid ester.
21. the composition of claim 1, wherein said phosphonic acid ester are the mixtures of at least a general formula (IV) phosphonic acid ester and at least a general formula (I), general formula (II) or general formula (III) phosphonic acid ester.
22. the composition of claim 14, wherein said phosphonic acid ester are N (CH 2PO 3M 2) 3And described phosphonic acid ester between about 50～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
23. the composition of claim 13, wherein said phosphonic acid ester is CH 3C (OH) (PO 3M 2) 2, and described phosphonic acid ester by the consumption of active acid between about 20～about 200ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
24. the composition of claim 12, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2And described phosphonic acid ester between about 10～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
25. the composition of claim 12, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, and described phosphonic acid ester by the consumption of active acid between about 30～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
26. the composition of claim 12, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N (CH 2PO 3M 2) 2And described phosphonic acid ester between about 10～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
27. the composition of claim 15, wherein said phosphonic acid ester is
Figure A028155020004C1
And described phosphonic acid ester between about 50ppm～about 500ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
28. the composition of claim 17, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2-N (CH 2PO 3M 2) 2, and be selected from N (CH 2PO 3M 2) 3, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The mixture of second phosphonic acid ester.
29. the composition of claim 28, wherein said second phosphonic acid ester is N (CH 2PO 3M 2) 3, and described mixture by the consumption of active acid between about 10～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
30. the composition of claim 28, wherein said second phosphonic acid ester is selected from (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, and described mixture by the consumption of active acid between about 20～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
31. the composition of claim 28, wherein said second phosphonic acid ester is selected from (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, and described mixture by the consumption of active acid between about 10～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
32. the composition of claim 17, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2With (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 20～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
33. the composition of claim 17, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2With N (CH 2PO 3M 2) 3Mixture, and described mixture by the consumption of active acid between about 30～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
34. the composition of claim 19, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2With N (CH 2PO 3M 2) 3Mixture, and described mixture by the consumption of active acid between about 50～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
35. the composition of claim 18, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N (CH 2PO 3M 2) 2With CH 3C (OH) (PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 10ppm～about 500ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
36. the composition of claim 18, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2With CH 3C (OH) (PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 30ppm～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
37. the composition of claim 1, the pH value of wherein said black liquor is 9 at least.
38. method that suppresses calcium salt scale in the alkali electroless pulping process, comprise: at least a phosphonic acid ester that in the black liquor of described chemical pulping process, adds effective scale suppression consumption, described composition comprises at least a phosphonic acid ester, is selected from the compound of following general formula:
M 2O 3P-CH 2-N(R 1)-(CH 2) m-N(R 2)-CH 2PO 3M 2???????????(I)
The compound of following general formula:
R 3-C(OH)(PO 3M 2) 2????????????????????????????????(II)
The compound of following general formula:
N-(CH 2PO 3M 2) 3???????????????????????????????????(III)
The phosphonic acid ester of following general formula:
The general formula (I) and (III) amine oxide of phosphonic acid ester,
Or its mixture, wherein M is independently selected from hydrogen, basic metal, alkaline-earth metal or ammonium, R 1And R 2Be independently selected from-CH 2PO 3M 2Or-(CH 2) n-N-(CH 2PO 3M 2) 2, m is 2 or 3, n is 2 or 3, R 3Be the alkyl group and the R of 1～17 carbon atom 3Be optional branching and optional undersaturated, condition is:
(a) this phosphonic acid ester is not the blend of general formula (II) phosphonic acid ester and general formula (III) phosphonic acid ester,
(b) this phosphonic acid ester is not general formula (II) phosphonic acid ester and general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2The blend of phosphonic acid ester,
(c) be selected from phosphonic acid ester, the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester or general formula (M 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, said composition does not contain nonionogenic tenside,
(d) be selected from the phosphonic acid ester or the general formula (M of general formula (III) when this phosphonic acid ester 2O 3P-CH 2) 2-N-(CH 2) 2-N-(CH 2PO 3M 2)-(CH 2) 2-N-(CH 2PO 3M 2) 2Phosphonic acid ester the time, this phosphonic acid ester greater than 25ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid, and
(e) when this phosphonic acid ester is selected from the phosphonic acid ester of general formula (IV), this phosphonic acid ester greater than 20ppm, is a benchmark with the black liquor weight that reclaims from pulp digester by the consumption of active acid.
39. the method for claim 38, wherein when M was basic metal, M was sodium or potassium.
40. the method for claim 38, wherein R 1And R 2Be CH 2PO 3M 2
41. the method for claim 40, wherein m is 2.
42. the method for claim 38, wherein R 1And R 2Be (CH 2) n-N-(CH 2PO 3M 2) 2
43. the method for claim 42, wherein m is 2, and n is 3.
44. the method for claim 38, wherein R 1Be CH 2PO 3M 2And R 2Be (CH 2) n-N-(CH 2PO 3M 2) 2
45. the method for claim 44, wherein m is 2, and n is 2.
46. the method for claim 38, wherein R 3It is the alkyl group of 1～5 carbon atom.
47. the method for claim 38, wherein R 3It is methyl.
48. the method for claim 38, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (I).
49. the method for claim 38, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (II).
50. the method for claim 38, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (III).
51. the method for claim 38, wherein said phosphonic acid ester are the phosphonic acid esters of at least a general formula (IV).
52. the method for claim 38, wherein said phosphonic acid ester are at least a general formula (I) and (III) amine oxide of phosphonic acid ester.
53. the method for claim 38, wherein said phosphonic acid ester are the mixtures of at least two kinds of general formulas (I) phosphonic acid ester.
54. the method for claim 38, wherein said phosphonic acid ester are the mixtures of at least a general formula (I) phosphonic acid ester and at least a general formula (II) phosphonic acid ester.
55. the method for claim 38, wherein said phosphonic acid ester are the mixtures of at least a general formula (I) phosphonic acid ester and at least a general formula (III) phosphonic acid ester.
56. the method for claim 38, wherein said phosphonic acid ester are the mixtures of at least two kinds of general formulas (II) phosphonic acid ester.
57. the method for claim 38, wherein said phosphonic acid ester are the mixtures of at least a general formula (IV) phosphonic acid ester and at least a general formula (I), general formula (II) or general formula (III) phosphonic acid ester.
58. the method for claim 50, wherein said phosphonic acid ester are N (CH 2PO 3M 2) 3And described phosphonic acid ester between about 50～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
59. the method for claim 49, wherein said phosphonic acid ester is CH 3C (OH) (PO 3M 2) 2, and described phosphonic acid ester by the consumption of active acid between about 20～about 200ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
60. the method for claim 48, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2And described phosphonic acid ester between about 10～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
61. the method for claim 48, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, and described phosphonic acid ester by the consumption of active acid between about 30～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
62. the method for claim 48, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N (CH 2PO 3M 2) 2And described phosphonic acid ester between about 10～about 1000ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
63. the method for claim 53, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2-N (CH 2PO 3M 2) 2,
Be selected from
N (CH 2PO 3M 2) 3, (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, or (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2The mixture of second phosphonic acid ester.
64. the method for claim 63, wherein said second phosphonic acid ester is N (CH 2PO 3M 2) 3, and described mixture by the consumption of active acid between about 10～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
65. the method for claim 63, wherein said second phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2, and described mixture by the consumption of active acid between about 20～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
66. the method for claim 63, wherein said second phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2, and described mixture by the consumption of active acid between about 10～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
67. the method for claim 53, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2With (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 20～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
68. the method for claim 53, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) 2With N (CH 2PO 3M 2) 3Mixture, and described mixture by the consumption of active acid between about 30～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
69. the method for claim 55, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2Be selected from N (CH 2PO 3M 2) 3The mixture of phosphonic acid ester, and described mixture by the consumption of active acid between about 50～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
70. the method for claim 54, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) CH 2CH 2CH 2N (CH 2PO 3M 2) 2With CH 3C (OH) (PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 10ppm～about 500ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
71. the method for claim 54, wherein said phosphonic acid ester is (M 2O 3PCH 2) 2NCH 2CH 2N (CH 2PO 3M 2) CH 2CH 2N (CH 2PO 3M 2) 2With CH 3C (OH) (PO 3M 2) 2Mixture, and described mixture by the consumption of active acid between about 30ppm～about 1000ppm, be benchmark with the black liquor weight that reclaims from described pulp digester.
72. the method for claim 51, wherein said phosphonic acid ester is
Figure A028155020010C1
And described phosphonic acid ester between about 50ppm～about 500ppm, is a benchmark with the black liquor weight that reclaims from described pulp digester by the consumption of active acid.
73. the method for claim 38, wherein said chemical pulping process is a sulphate process.
74. the method for claim 73, wherein calcium salt scale is suppressed in pulp digester.
75. the method for claim 73, wherein calcium salt scale pulp washing operation before floating is suppressed.
76. the method for claim 73, wherein calcium salt scale is suppressed in the black liquor recovery operation.
77. the method for claim 38, wherein said calcium salt are lime carbonate or calcium sulfate.
78. the method for claim 77, wherein said calcium salt is a lime carbonate.
79. the method for claim 38, the pH value of wherein said black liquor is 9 at least.
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JP4080994B2 (en) 2008-04-23
NO20035413D0 (en) 2003-12-05
EP1392610A1 (en) 2004-03-03
US7300542B2 (en) 2007-11-27
AU2002305842B2 (en) 2008-08-21
BR0210180A (en) 2004-04-27
AR036082A1 (en) 2004-08-11

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